Treatment of cracked hydrocarbon distillates



Patented July 15, 1941 TREATMENT or CRACKED HYDROCARBON DISTILLATES William J. Ryan, Wilmington, and Marcus T. Kendall, Long Beach, Calif., assignors to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Application March 24, 1939, Serial No. 263,944

4 Claims.

This invention relates to the chemical treatment of hydrocarbon oils and has to do particularly with the acid treatment and sweetening of cracked hydrocarbon distillates.

In the treatment of cracked hydrocarbon distillates, it is customary to use sulfuric acid of about 66 Baum gravity, having an acid concentration of about 93% H2SO4. The acid treated product (after separation of the acid sludge) is neutralized, rerun to separate high boiling point polymerized bodies and then the neutralized product must be treated with doctor solution in order to sweeten same.

The foregoing type of treatment is objectionable in that the acid is relatively non-selective and causes considerable loss of valuable products by excessive removal of desirable constituents along with the undesirable ones. Such an operation also has the disadvantage of producing high boiling sulfur containing compounds which impair the quality of the oil and make it obligatory to use the expensive doctor treatment (sodium plumbite) in order to convert the sour high boiling mercaptans into sweet disulfides.

We have found that the above objections may be overcome and the objects of our invention obtained by using certain treating reagents in the exact strength and operating in a particular manner.

An object of the invention is to selectively .re-

-move gum forming constituents without substantially affecting the other constituents of the oil.

A further object of the invention is to treat the oil to produce a product of the desired characteristics and containing substantially no high boiling polymerized products which normally require redistillation to effect separation thereof.

Another object of the invention is to carry out the acid treating operation in such a manner that a product is obtained which may be readily sweetened without resort to the conventional doctor treatment. w i

Another object of the invention is to provide means of sweetening in combination with the acid treating operation, whereby a finished prod not is produced much more economically and of improved quality.

In accordance with the invention, a cracked product, such as the cracked distillate from a cracking still, or a mixture of cracked products from several stills, or other sources of supply, is treated with diluted sulfuric acid of the exact strength to selectively remove only the unstable gum forming constituents which may comprise diolefins. The treated oil is then contacted with a strong alkali solution while under considerable superatmospheric pressureand at an elevated temperature. By properly choosing the correct strength of reagents and regulating the conditions of treatment, a stable sweet product may be obtained.

In practicing the invention, sulfuric acid of a concentration not greater than 60% H2804 should be used. We prefer about 57% for treating California distillates. It is intended that the acid be of such strength that only the unstable gum forming constituents are removed. It has been definitely ascertained that sulfuric acid treatment on cracked distillates of over 60% H2804 starts polymerization and even though slight, it increases the gum content and necessitates rerunning to remove this gum of polymerization.

It has been definitely ascertained that sulfuric acid treatment on cracked distillates of less than 55% H2SO4 fails to remove the substantial portion of the inherent gum (naturally present in the raw gasoline) and thus the gasoline, is unfit for commercial use.

On the other hand, it has been definitely ascertained that sulfuric acid of a strength between 55% and 60% H2SO4 has a particularly selective solvent action on cracked distillates in that it removes substantially all of the inherent gum and at the same time prohibits the formation of synthetic gum because of polymerization being prevented. For example: If the gum formation is due to diolefins, it is desirable to selectively remove these compounds without substantial polymerization of the olefin compounds. It has been found that a gum stable product may be obtained without measurable effect on other properties such as antiknock, color, etc.

The particular manner of applyingthe acid may be varied considerably Good results have been obtained by addingthe acid portion-wise. We. prefer-to use from 2 to 5 dumps of acid,

although in some cases it may be satisfactory to use only one dump. A total of about 2 to 12 pounds of acid per barrel of oil is ordinarily sufficient. Any well known or preferred method of contact may be used,such as orifice plates or mechanical mixers, although we prefer a fcounterflow type of operation. Ordinary temperatures may be used, although it is contemplated that cold acid treatment may be employed if desired.

The acid treated product, after separation of the acid sludge, is neutralized in the customary mannerwith aqueous caustic alkali or caustic soda. A caustic soda solution of about 5 degrees Baum gravity is ordinarily used. In some cases this preliminary neutralizing step may be omitted and the acid treatedproduct subjected directly to the hot alkali treatment described should be substantially free from high boiling polymerized products and as a result the end point should not be materially altered, whereby redistillation would be required. The product essentially is also free from sulfur compounds which are refractory and diflicultly treated. Accordingly, the product so previously treated is peculiarly adapted for the hot alkali treatment in place of the more expensive, customary doc tor treatment with sodium plumbite.

The alkali treating or sweetening step is carried out by contacting the oil by any suitable means with a strong alkali solution such as caustic soda. The strength of alkali may be varied and one skilled in the art will be able to determine the required strength to obtain the desired results.

We have found solutions varying from 20 to 50 degrees Baum gravity satisfactory, and prefer to use about 45 degrees gravity. The temperature of treatment should be at least about 150 degrees F. and may be as high as 300 degrees or more. We prefer temperatures around 200 to 210 degrees F.

The mixture is also maintained under a sub- It is essential for the success of the sweetening step of the invention that substantialy n polymerization takes place in the acid treating step. Without restricting the invention in any Way to a particular theory of reaction, it is believed that when polymerization occurs, high boiling point mercaptans are formed, which will not react with the caustic soda, even under the influence of heat and pressure, and as a result, normally would require the use of plumbite to convert them to disulfides. The present invention provids means for selectively dissolving the inherent gum and substantially preventing polymerization.

The invention is particularly advantageous for treating high sulfur content oils. It is simple and efhcient and eliminates the expensive doctor treating operation and substitutes a simple caustic treatment. The reagents, particularly the caustic solution, may be recovered and restored to substantially the original activity by releasing the pressure and steaming.

Instead of first acid treating the oil and then subjecting the acid treated product to the hot alkali treatment, it is sometimes advantageous to give the oil the hot alkali treatment prior to the acid treatment. It is contemplated, therefore, that the untreated oil may be first subjected to treatment with strong alkali substantially as described, the alkali treated product treated with the sulfuric acid and the acid treated product neutralized with dilute caustic solution to produce a finished product. For example, a cracked naphtha was treated at a temperatureof approximately 325 F. and under a pressure of about 175 lbs. with a caustic soda solution of approximately 25 Baum gravity, whereby the sulfur compounds were substantially removed. The treated naphtha was then subjected to the above described weak acid treatment. The acid treated product was then neutralized with a weaker caustic soda solution to produce a sweet, gum stable product of low sulfur content. 7

While we have specified caustic soda solution, it is contemplated that other compounds of the alkali metals or of the alkali earth metals are within the scope of the invention.

The present invention has the advantage over the conventional method of treatment in that the cost of chemicals is materially decreased, treating losses are reduced and the antiknock value of the finished product is increased. It has been found, for example, that treating costs may be reduced 50-75% by our invention; that treating losses may be as much as 60% lower and that the antiknock value of the finished product may be several points higher than normally obtained.

This is a continuation in part of application Serial No.148,260, filed June 15, 1937.

' scope thereof and therefore only such limitations subjecting the acid treated oil to the action of should be imposed as are indicated in the appended claims.

We claim:

1. A'process for the treatment of cracked petroleum hydrocarbon distillates of high sulfur content, which comprises subjecting the distillate to the action of sulfuric acid of about 55-60% strength wherebygumforming bodies are removed without substantially affecting other constituents and then treating the oil with caustic alkali solution at a temperature of at least about F. while under a substantial superatm-ospheric pressure, to remove sour sulfur compounds and produce a sweet product.

2. A process for the treatment of cracked petroleum hydrocarbon distillates of high sulfur content, "which comprises contacting the distillate with dilute sulfuric acid of about 55-60% concentration to remove gum forming constituents without substantially affecting other constituents of the oil, separating the acid sludge and then concentrated caustic alkali solution at a tempera'ture of about -l50300 F. while under a pressure of at least about 50 lbs. whereby gum forming bodies are removed without substantially affecting other constituents.

3. A process for the treatment of cracked petroleum hydrocarbon distillates of high sulfur content, which comprises contacting the distillate with sulfuric acid solution of about 55-60% trated caustic alkali solution at a temperature of about 150-300-F. while under a substantial superatmospheric pressure to remove sulfur-containing bodies and to produce a substantially sweet product.

4. A process for the treatment of cracked petroleum'hydrocarbon distillates of high sulfur content, which comprises treating the distillate with sulfuric acid of about 57% concentration whereby unstable gum forming constituents are removed without substantially affecting other constituents of the oil, separating the acid sludge, neutralizing the acid oil and then contacting the oil with concentrated caustic alkali solution of about 2,050% concentration at a temperature ofabout 200? F. while under a pressure in excess of 50 lbs. whereby sour sulfur compounds are removed and a sweet product produced.

7 WILLIAM J. RYAN.

MARCUS T. KENDALL. 

